This disclosure relates to electrochemical cell systems, and, more particularly, to an electrochemical cell in which the flow field support structures comprise porous plates that enable high pressures to be maintained across the cell.
Electrochemical cells are energy conversion devices, usually classified as either electrolysis cells or fuel cells. Proton exchange membrane electrolysis cells can function as hydrogen generators by electrolytically decomposing water to produce hydrogen and oxygen gases. Referring to
An electrolysis cell system may include a number of individual cells arranged in a stack with reactant water being directed through the cells via input and output conduits formed within the stack structure. The cells within the stack are sequentially arranged, and each one includes a membrane electrode assembly (MEA) defined by a proton exchange membrane disposed between a cathode and an anode. The cathode, anode, or both may be gas diffusion electrodes that facilitate gas diffusion to the proton exchange membrane. Each membrane electrode assembly is in fluid communication with flow fields adjacent to the membrane electrode assembly, defined by structures configured to facilitate fluid movement and membrane hydration within each individual cell.
The portion of water discharged from the cathode side of the cell, which is entrained with hydrogen gas, is fed to a phase separator to separate the hydrogen gas from the water, thereby increasing the hydrogen gas yield and the overall efficiency of the cell in general. The removed hydrogen gas may be fed either to a dryer for removal of trace water, to a storage facility, e.g., a cylinder, a tank, or a similar type of containment vessel, or directly to an application for use as a fuel.
Another type of water electrolysis cell that utilizes the same configuration as is shown in
A typical fuel cell also utilizes the same general configuration as is shown in
A typical cell system that can be utilized with other cells and incorporated into a stack structure is shown at 30 with reference to
A pressure pad 52 is typically disposed between flow field support member 50 and a cell separator plate 54. A pressure pad separator plate 62 may be disposed between pressure pad 52 and flow field support member 50. Pressure pads may be disposed on either or both sides of membrane 32 and may be positioned within either or both of the flow fields of cell system 30. One or more pressure plates 60 may optionally be disposed adjacent to pressure pad 52 to distribute the pressure exerted on pressure pad 52 and increase the pressure within the cell environment. Flow field support member 50 and pressure pad 52 (as well as optional pressure plates 60) are retained within flow field 40 by a frame 56 and cell separator plate 54. A gasket 58 is optionally positioned between frame 56 and cell separator plate 54 to effectively seal flow field 40. The cell components, particularly frames 44, 56, cell separator plates 48, 54, and gaskets 46, 58, are formed with the suitable manifolds or other conduits to facilitate fluid communication through cell system 30.
Under high pressure operating conditions, flow field support members 42, 50 oftentimes do not provide the necessary structural integrity to the MEA. For example, during operation of a cell in which a differential pressure across the MEA exceeds about 400 pounds per square inch (psi), the ion exchange membrane from which the MEA is fabricated can extrude into the screen mesh on the side of the MEA having the lower pressure, thereby potentially causing a malfunction of cell system 30. Moreover, and because the screens are characterized by a structure having a relatively large mesh size, flow through the screen is oftentimes directed in channels from the inlet to the outlet such a less-than-uniform distribution of fluid is effected across the support structure (and thus across the cross-section of the cell to the electrode).
While existing electrolysis cell systems are suitable for their intended purposes, there still remains a need for improvements. Some of the improvements needed include the use of flow field support members of sufficient structural integrity to withstand high pressures associated with the operation of the cell systems and the provision of the uniform distribution of flow across the cell.
Disclosed herein are electrochemical cells and methods for using the same. In one embodiment, the electrochemical cell comprises: a first electrode and a second electrode with a membrane disposed therebetween and in ionic communication with the first electrode and the second electrode and a sintered porous support member disposed on a side of the membrane opposite the second electrode, wherein the support member comprises a first portion on first side of the support member proximate the membrane and a second portion disposed on a side of the first portion opposite the membrane, wherein the second portion has a second portion porosity different from a first portion porosity.
In another embodiment, the An electrochemical cell, comprising: a first electrode and a second electrode with a membrane disposed therebetween and in ionic communication with the first electrode and the second electrode, a flow field consisting essentially of a porous support member disposed in electrical and physical communication with the first electrode, wherein the porous support member comprises a channel, and a pressure assembly disposed in physical and electrical communication with the flow field.
In one embodiment, the method for operating the electrochemical cell comprises: passing water through a sintered porous support member to a first electrode, producing hydrogen ions and oxygen, moving the hydrogen ions across a membrane to a second electrode, wherein there is a pressure differential across the membrane of greater than or equal to about 100 psi, and forming hydrogen gas at the second electrode. The support member can be disposed on a side of the membrane opposite the second electrode, wherein the support member comprises a first portion on first side of the support member proximate the membrane and a second portion disposed on a side of the first portion opposite the membrane, and wherein the second portion has a second portion porosity different from a first portion porosity.
In another embodiment, the method for operating an electrochemical cell comprises: passing water through a flow field to a first electrode, producing hydrogen ions and oxygen, moving the hydrogen ions across a membrane to a second electrode, wherein there is a pressure differential across the membrane of greater than or equal to about 100 psi, and forming hydrogen gas at the second electrode. The flow field consists essentially of a sintered porous support member disposed in electrical and physical communication with the first electrode, and a pressure assembly is disposed in physical and electrical communication with the flow field.
The above described and other features are exemplified by the following figures and detailed description.
Referring now to the drawings wherein like elements are numbered alike in several Figures:
Disclosed herein is a support structure for an electrochemical cell, which can serve as both a membrane support and the flow field. The cell into which the support structure may be incorporated may be operated as an electrolysis cell and/or a fuel cell. While the discussion below is directed to an anode feed electrolysis cell, however, it should be understood that cathode feed electrolysis cells, fuel cells, and regenerative fuel cells are also within the scope of the embodiments disclosed.
A cell stack is formed of a plurality of individual cells and includes flow field support structures disposed in the flow fields at opposing sides of a membrane electrode assembly (MEA) comprising a membrane and electrodes. One of the electrodes provides reactive sites for the electrolysis of water, with one or more of the electrodes optionally comprising a porous catalytic structure. The flow field support structures are porous members (e.g., sintered porous support members), generally in the form of plates, that are disposed within the flow fields such that the members are adjacent to and in electrical contact with an electrode and a boundary surface defined by either a cell separator plate, a pressure pad, a screen pack (e.g., an additional flow field), or a pressure pad separator plate. Optionally, the electrode can be disposed in the porous support member, either throughout the member or mostly on the side of the member disposed proximate the membrane.
Referring now to
Cell 70 comprises a porous plate support member 72 disposed at an MEA 76 of cell 70. Optionally, cell 70 may further include a porous plate support member 74 disposed at the opposing side of cell 70, as is shown, with a pressure pad 78 disposed adjacent one or both of the support members 72,74, and an optional pressure pad separator plate (not shown) disposed between the pressure pad 78 and the adjacent support member (72/74). MEA 76 comprises a proton exchange membrane 86 and the electrodes (anode 88 and cathode 90) disposed at opposing sides of proton exchange membrane 86. As shown, both anode 88 and cathode 90 are positioned in contact (e.g., ionic communication) with the surface of proton exchange membrane 86 within the active areas, which are defined as the areas of an electrolysis cell at which the dissociation of water and production of an oxygen gas stream and/or a hydrogen gas stream.
Membrane 86 comprises electrolytes that are preferably solids under the operating conditions of the electrochemical cell. Useful materials from which membrane 86 can be fabricated include proton conducting ionomers and ion exchange resins. Useful proton conducting ionomers include complexes comprising an alkali metal salt, an alkali earth metal salt, a protonic acid, a protonic acid salt, or the like, as well as combinations at least one of the foregoing materials. Counter-ions useful in the above salts include halogen ion, perchloric ion, thiocyanate ion, trifluoromethane sulfonic ion, borofluoric ion, and the like, as well as combinations comprising at least one of the foregoing materials. Representative examples of such salts include, but are not limited to, lithium fluoride, sodium iodide, lithium iodide, lithium perchlorate, sodium thiocyanate, lithium trifluoromethane sulfonate, lithium borofluoride, lithium hexafluorophosphate, phosphoric acid, sulfuric acid, trifluoromethane sulfonic acid, and the like, as well as combinations comprising at least one of the foregoing materials. The alkali metal salt, alkali earth metal salt, protonic acid, or protonic acid salt is complexed with one or more polar polymers such as a polyether, polyester, or polyimide, or with a network or cross-linked polymer containing the above polar polymer or combination of polymers as a segment. Useful polyethers include polyoxyalkylenes, such as polyethylene glycol, polyethylene glycol monoether, and polyethylene glycol diether; copolymers of at least one of these polyethers, such as poly(oxyethylene-co-oxypropylene)glycol, poly(oxyethylene-co-oxypropylene)glycol monoether, and poly(oxyethylene-co-oxypropylene)glycol diether; condensation products of ethylenediamine with the above polyoxyalkylenes; and esters, such as phosphoric acid esters, aliphatic carboxylic acid esters or aromatic carboxylic acid esters of the above polyoxyalkylenes. Copolymers of, e.g., polyethylene glycol with dialkylsiloxanes, maleic anhydride, or polyethylene glycol monoethyl ether with methacrylic acid, exhibit sufficient ionic conductivity to be useful.
Ion-exchange resins useful as proton conducting materials include hydrocarbon- and fluorocarbon-type resins. Hydrocarbon-type ion-exchange resins include phenolic resins, condensation resins such as phenol-formaldehyde, polystyrene, styrene-divinyl benzene copolymers, styrene-butadiene copolymers, styrene-divinylbenzene-vinylchloride terpolymers, and the like, that are imbued with cation-exchange ability by sulfonation, or are imbued with anion-exchange ability by chloromethylation followed by conversion to the corresponding quaternary amine.
Fluorocarbon-type ion-exchange resins can include hydrates of tetrafluoroethylene-perfluorosulfonyl ethoxyvinyl ether or tetrafluoroethylene-hydroxylated (perfluoro vinyl ether) copolymers. When oxidation and/or acid resistance is desirable, for instance, at the cathode of a fuel cell, fluorocarbon-type resins having sulfonic, carboxylic and/or phosphoric acid functionality are preferred. Fluorocarbon-type resins typically exhibit excellent resistance to oxidation by halogen, strong acids, and bases. One family of fluorocarbon-type resins having sulfonic acid group functionality is NAFION® resins (commercially available from E. I. du Pont de Nemours and Company, Wilmington, Del.).
Anode 88 and cathode 90 are fabricated from catalytic materials suitable for performing the needed electrochemical reaction (e.g., electrolyzing water to produce hydrogen and oxygen). Suitable catalytic materials for anode 88 and cathode 90 include, but are not limited to, platinum, palladium, rhodium, carbon, gold, tantalum, tungsten, ruthenium, iridium, osmium, and the like, as well as alloys and combinations comprising at least one of the foregoing materials. Anode 88 and cathode 90 are positioned adjacent to and in ionic communication with membrane 86 and defined by structures comprising discrete catalytic particles adsorbed onto a porous substrate. Adsorption of the catalytic particles onto the substrate may be by any method including, but not limited to, spraying, dipping, painting, imbibing, vapor depositing, combinations comprising at least one of the foregoing methods, and the like. Alternately, the catalytic particles may be deposited directly onto opposing sides of membrane 86 or in/onto porous plate support members 72, 74.
Porous support member 72 is defined by a thickness t and at least one lengthwise dimension d such that porous support member 72 occupies substantially all of the volume of the cavity defining the flow field. Although only porous support member 72 is described, a porous support member 74 should be understood to be substantially similar in construction. It is noted, however, that the design of each of the porous support members is determined independently of the other porous support member (e.g., one or more of the members may comprise multiple layers, a porosity gradient(s), channel(s), areas of higher and lower porosity, as well as combinations comprising at least one of these designs).
The geometry and composition of the porous support member 72 can vary depending upon the particular type and geometry of the electrochemical cell in which the porous support member 72 is utilized. The geometry of porous support member 72 is preferably such that the porous support member 72 can be retained within the frames of an electrolysis cell. With respect to composition, the porous plate member 72 is preferably fabricated of a material such that electrical communication can be maintained between opposing surfaces of porous plate support member 72 and across cell 70. Materials from which the plates may be fabricated include metals such as sintered metals. Possible metals include, but are not limited to, titanium, niobium, zirconium, carbon, hafnium, iron, cobalt, nickel, and the like, as well as alloys and combinations comprising at least one of the foregoing materials, such as nickel alloys, iron alloys (e.g., steels such as stainless steels and the like), cobalt alloys, and the like. Various material forms can also be employed, including fibrous (e.g., random, woven, non-woven, chopped, continuous, and the like), granular, particulate powder, combinations comprising at least one of the foregoing forms, and the like. Alternately, the materials may be in the forms of fibrous felts, woven- or unwoven screens, combinations comprising at least one of the foregoing forms, and the like.
In the embodiment illustrated in
The manufacture of a porous support member comprises sintering a layer of electrically conductive material to form a porous support. Depending upon the desired design of the porous support member, the sintered layer can have a substantially uniform porosity throughout, a porosity gradient (e.g., from one side toward another where the area of lowest porosity can be on a side of the porous support member or within (e.g., toward the center) thereof), and/or areas of higher and lower porosity (wherein porosity is the pore volume versus the total volume of that portion). If multiple layers form the porous support member, each portion 92, 94, 96 is maintained in electrical communication with its adjacent portion. Maintenance of electrical communication can be by various techniques, some exemplary techniques include bonding (e.g., diffusion bonding), welding (e.g., spot- or tack welding), pressure, and the like.
In still another embodiment, a single sintered porous support member can be manufactured such that a higher density region can be formed at a surface of the substrate disposed proximate the membrane (e.g., adjacent to and in contact with the electrode). A porous plate support member having such a higher density region adjacent to the membrane provides added support to the membrane (note, the electrode can be disposed on/within the porous support member and/or on the membrane, between the porous support member and the membrane).
One exemplary multi-plate configuration of porous plate member 72 comprises an optional first portion (e.g., the side of the porous support member opposite the membrane side) 92 (e.g., portion of a single layer or the entire layer) having a first portion density, a second portion 94 (e.g., the inside portion of the porous support member or the side opposite the membrane side if no third portion exists) having a second portion density different from the first portion density (i.e., a different porosity). For example, the second portion density can be lower than, equal to, or greater than the first portion density, and a third portion (e.g., the membrane side portion) 96 can have a third portion density that is greater than the second portion density, with a density commensurate with the first portion density possible. For example, the first portion porosity can be equal to either the second portion porosity, the third portion porosity, or can be different. The third portion porosity can be less than or equal to about 60%, e.g., about 35% to about 50%. The second portion porosity can be greater than or equal to about 50%, e.g., about 50% to about 70%, and the first portion porosity can be greater than or equal to about 35%, e.g., about 35% to about 70%.
Referring now to
Referring now to
Referring to
Second portion 94 is shown with reference to
In the exemplary embodiment in which second portion 94 (which can comprise a uniform density) is of a variable density, second portion 94 comprises a region 114 of high density material that extends, for example, from a point at an edge of second portion 94 that corresponds to the inlet to a point at the edge of second portion 94 that corresponds to the outlet. The high density material has a porosity of greater than or equal to about 50%, preferably about 50% to about 60%, and more preferably about 50%. Disposed along edges of region 114 are a first region 116 of lower density material and a second region 117 of lower density material. The lower density material has a porosity of greater than or equal to about 60%, which allows for a higher flow rate of water through the cell, thereby providing for increased cooling capacity within the cell. It is understood that the use of the variable density can be used in conjunction with, or as an alternative to, the use of channel(s) (e.g., in second portion 94 and/or in first portion 92). If the second portion 94 is disposed on the side of the porous support member 72 opposite the membrane side, the second portion 92 may have the channel configurations discussed above for the first portion 92. Additionally, even if the first portion 92 is employed, the second portion 94 may comprise channels and/or regions of higher and lower porosity to facilitate fluid transfer and/or cell cooling.
Referring now to
Various combinations of support members may also be incorporated into an electrochemical cell configuration. In particular, porous support member 72 may be disposed at an oxygen side of an electrolysis cell 70 in which anode 88 is disposed at the oxygen side of membrane 86, cathode 90 is disposed at a hydrogen side of membrane 86, and porous plate support member 74 is disposed at cathode 90 at the hydrogen side of cell 70, as is shown in
In any embodiment, elimination of other types of flow field support structures (e.g., screen packs and the like) and their replacement with the above-described porous support members, at either or both sides of the cell, enable the cell to operate at high pressures (e.g., at about 500 psi or greater) without deformation of the support structures. Furthermore, the incorporation of the porous support members imparts an improved structural integrity to the cell, which thereby allows the cell to be operated more efficiently under pressure of about 100 psi to about 300 psi and more.
A method for operating an electrochemical cell with the porous support members can comprise passing water through a sintered porous support member to a first electrode to produce hydrogen ions and oxygen. The hydrogen ions are moved across the membrane to a second electrode where hydrogen gas is formed at the second electrode. Preferably, the pressure differential across the membrane is greater than or equal to about 100 psi, with greater than or equal to about 500 psi, and even greater.
A method of hydrating an electrode of an electrochemical cell can comprise receiving a fluid stream at a first layer of a porous support member, diffusing fluid from a fluid stream through a first layer to a second layer of the porous support member, and diffusing fluid from the second layer to the electrode. The diffusing of the fluid from the second layer to the electrode comprises diffusing fluid through a third layer of the porous support member.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the disclosure.
This application is a continuation of U.S. patent application Ser. No. 10/604,670, filed on Aug. 8, 2003, which is a continuation-in-part of prior U.S. patent application Ser. No. 09/965,630, filed on Sep. 27, 2001, which claims priority to U.S. Provisional Patent Application Ser. No. 60/235,743 filed on Sep. 27, 2000, U.S. Provisional Patent Application 60/235,821 filed on Sep. 27, 2000 and U.S. Provisional Application 60/235,974 filed on Sep. 28, 2000.
Number | Date | Country | |
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60235974 | Sep 2000 | US | |
60235821 | Sep 2000 | US | |
60235743 | Sep 2000 | US |
Number | Date | Country | |
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Parent | 10604670 | Aug 2003 | US |
Child | 12249247 | US |
Number | Date | Country | |
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Parent | 09965630 | Sep 2001 | US |
Child | 10604670 | US |